US6815053B2 - Lowly heat-expandable laminate - Google Patents

Lowly heat-expandable laminate Download PDF

Info

Publication number
US6815053B2
US6815053B2 US10/221,373 US22137303A US6815053B2 US 6815053 B2 US6815053 B2 US 6815053B2 US 22137303 A US22137303 A US 22137303A US 6815053 B2 US6815053 B2 US 6815053B2
Authority
US
United States
Prior art keywords
resin
laminated plate
weight
thermal expansion
low thermal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime, expires
Application number
US10/221,373
Other versions
US20040096680A1 (en
Inventor
Tomoko Inoue
Hiroya Okumura
Isao Hirata
Shigehiro Okada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Electric Works Co Ltd
Japan Composite Co Ltd
Original Assignee
Japan Composite Co Ltd
Matsushita Electric Works Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Composite Co Ltd, Matsushita Electric Works Ltd filed Critical Japan Composite Co Ltd
Assigned to MITSUI TAKEDA CHEMICALS, INC. reassignment MITSUI TAKEDA CHEMICALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INOUE, TOMOKO, OKUMURA, HIROYA
Assigned to MATSUSHITA ELECTRIC WORKS, LTD. reassignment MATSUSHITA ELECTRIC WORKS, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HIRATA, ISAO, OKADA, SHIGEHIRO
Assigned to JAPAN COMPOSITE CO., LTD. reassignment JAPAN COMPOSITE CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MITSUI TAKEDA CHEMICALS INC.
Publication of US20040096680A1 publication Critical patent/US20040096680A1/en
Application granted granted Critical
Publication of US6815053B2 publication Critical patent/US6815053B2/en
Assigned to PANASONIC ELECTRIC WORKS CO., LTD. reassignment PANASONIC ELECTRIC WORKS CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: MATSUSHITA ELECTRIC WORKS, LTD.
Adjusted expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2398/00—Unspecified macromolecular compounds
    • B32B2398/20—Thermoplastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/12—Ships
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0212—Resin particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/06—Thermal details
    • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904—Staple length fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • the present invention relates to a laminated plate having a low thermal expansion and excellent toughness, heat resistance and water resistance, particularly to a composite laminated plate.
  • a cured article of a radically polymerizable resin such as unsaturated polyester resins or vinyl ester resins has a well-balanced performance with regard to the mechanical, chemical and electric characteristics, and has been employed widely in the fields of housing, shipping and automobile industries.
  • a cured article of such a radically polymerizable resin when it is applied to a laminated plate for a print circuit board or a insulating plate while utilizing its excellent heat resistance, water resistance and electric characteristics, poses an insufficiency of the toughness and the impact resistance for the plate and undergoes problematic cracking or delamination between the fiber-reinforced layers during a punching process.
  • a liquid rubber component is added to the resin for enhancement of toughness, but a cured article of the resin containing a rubber component has a high thermal expansion rate, which is not always suitable for a laminated plate used under elevated temperature.
  • An objective of the present invention is to provide a laminated plate, especially a composite laminated plate, which is obtained from a resin composition whose main component is a radically polymerizable resin, which has excellent toughness, heat resistance and water resistance, which has such a low thermal expansion rate as a average linear expansion coefficient (10 ⁇ 6 /° C.) of not higher than 20 within the temperature range from 40 to 150° C., which can be processed and used at an elevated temperature, and which can be produced at a lower cost but can exert a performance comparable with a conventional expensive material such as an epoxy resin.
  • the present invention is:
  • thermosetting resin composition comprising (a) a radically polymerizable resin, (b) a thermoplastic resin, (c) a radically polymerizable monomer and (d) an inorganic filler, wherein (a) is present in an amount of 10 to 75 parts by weight, (b) is present in an amount of 2 to 30 parts by weight, (c) is present in an amount of 20 to 60 parts by weight and (d) is present in an amount of 5 to 250 parts by weight, based on 100 parts by weight of the total weight of (a), (b) and (c).
  • thermoplastic resin (b) is not higher than 60° C.
  • thermoplastic resin (b) is a saturated polyester resin whose glass transition point is not higher than 60° C.
  • thermoplastic resin (b) is a saturated polyester resin whose glass transition point is not higher than 60° C. and whose number average molecular weight is 2,000 to 100,000.
  • a low thermal expansion laminated plate according to any one of the above-mentioned 1 to 6 wherein the laminated material of the fiber-reinforced layers is a composite laminated material comprising as a surface layer a glass fiber woven fabric impregnated with a thermosetting resin composition laminated with an inner lining layer which is a glass fiber non-woven fabric impregnated with a thermoplastic resin composition.
  • a radically polymerizable resin (a) employed in the present invention is not particularly limited as long as it is a resin having an ethylenically unsaturated bond
  • those employed preferably are a vinyl ester resins produced by adding ethylenically unsaturated monobasic acid to an epoxy resin and an unsaturated polyester resin produced by a dehydration condensation reaction between a dicarboxylic acid which should contain an ⁇ , ⁇ -olefinic unsaturated dicarboxylic acid or an anhydride thereof and a diol.
  • the epoxy resin as a starting material for a vinyl ester resin may for example be those disclosed in Japanese Patent Application Laid-open No.110948 (1997), such as a bisphenol epoxy resin including bisphenol A and bisphenol F, a novolac epoxy resin including phenol novolac [e.g., YDPN638, produced by TOTO KASEI CO. LTD., epoxy equivalent: 200] and cresol novolac [e.g., YDCN702P, produced by TOTO KASEI CO. LTD., epoxy equivalent: 200], an aliphatic epoxy resin, a nitrogen-containing epoxy resin (e.g., triglycidyl isocyanurate), a copolymeric epoxy resin and the like.
  • a bisphenol epoxy resin including bisphenol A and bisphenol F e.g., YDPN638, produced by TOTO KASEI CO. LTD., epoxy equivalent: 200
  • cresol novolac e.g., YDCN702P, produced by TOTO KASEI CO.
  • An ethylenically unsaturated monobasic acid may for example be an unsaturated monocarboxylic acid such as (meth)acrylic acid as well as a reaction product between a polybasic acid anhydride and a compound having at least one (meth)acrylic double bond and an alcoholic OH group simultaneously in one molecule.
  • unsaturated monocarboxylic acid such as (meth)acrylic acid as well as a reaction product between a polybasic acid anhydride and a compound having at least one (meth)acrylic double bond and an alcoholic OH group simultaneously in one molecule.
  • a compound having at least one (meth)acrylic double bond and an alcoholic OH group simultaneously may for example be a reaction product between hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, pentaerythritol tri (meth)acrylate, glycerin di (meth)acrylate, (meth) acrylic acid and a polyhydric alcohol.
  • (meth)acrylic acid is preferred.
  • the reaction between an epoxy resin and an ethylenically unsaturated monobasic acid described above may be conducted by a known method.
  • the reaction is conducted at 80 to 150° C. for 1 to 20 hours in the presence of a polymerization inhibitor such as hydroquinone and a catalyst such as a tertiary amine e.g., benzyldimethylamine or a phosphorus compound e.g., triphenylphosphine, whereby obtaining an intended vinyl ester resin.
  • a polymerization inhibitor such as hydroquinone
  • a catalyst such as a tertiary amine e.g., benzyldimethylamine or a phosphorus compound e.g., triphenylphosphine
  • reaction between the epoxy group and the carboxyl group in the vinyl estrification reaction is a 1 to 1 equivalent reaction
  • the synthesis may sometimes be conducted also with an excess of the epoxy group or with an excess of the carboxyl group.
  • An unsaturated polyester resin employed in the present invention can be synthesized by condensation between an ⁇ , ⁇ -olefinic unsaturated dicarboxylic acid and a glycol.
  • a saturated dicarboxylic acid, aromatic dicarboxylic acid or dicyclopentadiene capable of reacting with a dicarboxylic acid may also be employed in the synthesis of the unsaturated polyester resin.
  • An ⁇ , ⁇ -olefinic unsaturated dicarboxylic acid may for example be maleic acid, fumaric acid, itaconic acid, citraconic acid and anhydrides of these dicarboxylic acids.
  • a dicarboxylic acid capable of being used together with such an ⁇ , ⁇ -olefinic unsaturated dicarboxylic acid may for example be adipic acid, sebacic acid, succinic acid, gluconic acid, o-, m-, p-phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and the like.
  • a glycol may for example be an alkane diol, oxa-alkane diol, a diol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A.
  • a monohydric or trihydric alcohol may also be employed.
  • An alkane diol may for example be ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, hydrogenated bisphenol A and the like.
  • An oxa-alkane diol may for example be dioxyethylene glycol and triethylene glycol.
  • a monohydric or trihydric alcohol used together with the glycols mentioned above may for example be octylalcohol, benzylalcohol, trimetylolpropane and the like.
  • the synthesis of an unsaturated polyester resin is conducted generally under heating, while water generated as a by-product being removed.
  • the Tg of an unsaturated polyester resin can be lowered by selecting starting materials to reduce the crosslink density and the reactivity of the resin, or by starting from adipic acid or sebacic acid as a saturated acid and diethylene glycol or dipropylene glycol as a glycol, those have a long chain molecular structure.
  • the Tg of the resin can be elevated by selecting starting material to increase the crosslink density or the reactivity of a resin or by starting from hydrogenated bisphenol A as a glycol which has a rigid structure.
  • the amount of a radically polymerizable resin (a) to be used is usually 10 to 75 parts by weight, preferably 30 to 67 parts by weight based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
  • the amount of a thermoplastic resin (b) employed in the present invention may for example be a thermoplastic resin used customarily as a low profile agent in an unsaturated polyester resin.
  • a thermoplastic resin may for example be polybutadiene or a hydrogenated derivative thereof, polyisoprene or a hydrogenated derivative thereof, aromatic vinyl/conjugated diene block copolymer or a hydrogenated derivative thereof, polystyrene, styrene/vinyl acetate block copolymer, polyvinyl acetate, polymethyl methacrylate, as well as a saturated polyester resin, polyether resin and the like.
  • an aromatic vinyl/conjugated diene block copolymer and saturated polyester resin are preferred, with a saturated polyester resin being particularly preferred.
  • the saturated polyester resin as a thermoplastic resin is not limited particularly, it preferably has a Tg of 60° C. or lower, more preferably 50° C. or lower. A Tg of the saturated polyester resin higher than 60° C. may be led to a difficulty in reducing the thermal expansion rate of a cured article sufficiently.
  • a saturated polyester resin may typically be those employed as single component anti-shrinkage agents for SMC and the like, for example, those synthesized from a dicarboxylic acid such as terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and the like and a diol such as ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexandiol, diethylene glycol, dipropylene glycol, and the like.
  • a dicarboxylic acid such as terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and the like
  • a diol such as ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexandiol, diethylene glycol, dipropylene glycol, and the like.
  • the molecular weight of a saturated polyester resin is not limited particularly, the number average molecular weight is usually 2,000 to 100,000, preferably 3,000 to 30,000, since a too lower molecular weight leads to a reduced heat resistance while a too higher molecular weight leads to a high viscosity.
  • a saturated polyester resin may for example be TTK-101 (produced by TAKEDA CHEMICAL INDUSTRIES LTD.) and BYLON 300, 630, 550 (produced by TOYOBO CO., LTD.).
  • thermoplastic resin (b) An aromatic vinyl/conjugated diene block copolymer is also a preferred example of the thermoplastic resin (b).
  • An aromatic vinyl/conjugated diene block copolymer may be a block copolymer known per se, and can be synthesized by block copolymerizing an aromatic vinyl monomer such as styrene, chlorostyrene and vinyl toluene with a conjugated diene monomer such as butadiene and isoprene by a conventional polymerization method.
  • a block copolymer may for example be styrene/isoprene block copolymer.
  • Such a block copolymer has a molar ratio of an aromatic vinyl monomer and a conjugated diene monomer of about 50:50 to 5:95 and an average molecular weight of about 30,000 to 200,000.
  • the amount of a thermoplastic resin (b) to be incorporated is usually 2 to 30 parts by weight, preferably 2 to 20 parts by weight based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
  • a radically polymerizable monomer (c) may for example be an unsaturated fatty acid such as acrylic acid and methacrylic acid, an unsaturated carboxylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-hydroxtethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and dodecyl acrylate, a nitrogen-containing monomer such as (meth)acrylamide and (meth)acrylonitrile, an aromatic vinyl compound such as styrene, vinyltoluene, divinylbenzene and p-t-butylstyrene and a polyfunctional (meth)acrylate such as ethylene glycol di(meth)acryl
  • the amount of a radically polymerizable monomer (c) to be incorporated is usually 20 to 60 parts by weight, preferably 25 to 55 parts by weight based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
  • An inorganic filler (d) employed in a thermosetting resin composition of the present invention may for example be aluminium hydroxide, glass powder, calcium carbonate, talc, silica, clay, glass balloon and the like. These may be used in an amount usually of 5 to 250 parts by weight, preferably 5 to 200 parts by weight, based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
  • the toughness and the low thermal expansion performance of a laminated plate can further be improved by incorporating a polymer fine particle (e) to a thermosetting resin composition employed in the present invention.
  • a polymer fine particle (e) preferably has a multilayer structure, although a monolayer particle may also be employed.
  • Such a multilayer polymer fine particle can be obtained by a consecutive multi-stage emulsion polymerization in which, in the presence of the preceding stage polymer, the subsequent stage monomer is subjected sequentially to seed polymerization, as is disclosed in JP-A-8-48704. That is, seed latex is first prepared by emulsion polymerization, then a monomer for forming the first layer is added and subjected to the seed polymerization.
  • a monomer for forming the second layer is added and subjected to the seed polymerization whereby synthesizing the second layer, and this procedure is repeated until the outermost layer is synthesized, whereby obtaining an intended multilayer-structured polymer.
  • a reactive unsaturated monomer employed in the seed polymerization of a polymer layer of a polymer fine particle (e) employed in the present invention may be any monomer having in the molecule thereof at least one reactive unsaturated bond, including a conjugated diene such as butadiene, isoprene and chloroprene, an alkyl acrylate such as ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, isononyl acrylate and 2-ethylhexyl acrylate and an alkyl methacrylate such as methyl methacrylate, ethyl methacrylate and cyclohexyl methacrylate.
  • a conjugated diene such as butadiene, isoprene and chloroprene
  • an alkyl acrylate such as ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl
  • any of these may be copolymerized with a monomer capable of being copolymerized with it, for example, an aromatic vinyl or aromatic vinylidene such as styrene, vinyltoluene and ⁇ -methylstyrene, a vinyl cyanide or vinylidene cyanide such as acrylonitrile and methacrylonitrile, an alkyl methacrylate such as methyl methacrylate and butyl methacrylate and an aromatic (meth) acrylate such as benzyl acrylate and phenoxyethyl acrylate.
  • an aromatic vinyl or aromatic vinylidene such as styrene, vinyltoluene and ⁇ -methylstyrene
  • a vinyl cyanide or vinylidene cyanide such as acrylonitrile and methacrylonitrile
  • an alkyl methacrylate such as methyl methacrylate and butyl methacrylate
  • an aromatic (meth) acrylate such as
  • a specific amount of a crosslinking monomer and grafting monomer can be employed as a copolymeric monomer in addition to the monomers described above.
  • the crosslinking monomer may be employed in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight based on the monomers forming the polymer, while the grafting monomer may be employed in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight based on the monomers forming the polymer layer.
  • a crosslinking monomer employed in the present invention is one having in its molecule at least two similar polymerizable groups, including an aromatic divinyl compound such as divinylbenzene and an alkane polyol polyacrylate or alkane polyol polymethacrylate such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimetacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate.
  • an aromatic divinyl compound such as divinylbenzene
  • an alkane polyol polyacrylate or alkane polyol polymethacrylate such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glyco
  • a grafting monomer employed in the present invention has at least two polymerizable groups having a different reactivity from each other in its molecule, for example an unsaturated carboxylic acid allyl ester such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate.
  • unsaturated carboxylic acid allyl ester such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate.
  • allyl methacrylate is particularly preferred.
  • a polymer fine particle (e) employed in the present invention can serve to further improve the toughness of a resin composition by modifying the outermost layer with a carboxyl group- or hydroxy group-carrying monomer.
  • a carboxyl group-carrying monomer may for example be acrylic acid, methacrylic acid, maleic acid and itaconic acid.
  • a hydroxy group-carrying monomer may for example be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 2-hydroxybutyl (meth)acrylate.
  • methacrylic acid is a preferred carboxyl group-carrying monomer
  • 2-hydroxyethyl methacrylate is a preferred hydroxyl group-carrying monomer.
  • the amount of such a functional group-carrying monomer is less than 10% by weight, preferably less than 5% by weight based on the monomers forming the outermost layer.
  • An amount of the functional group carrying monomer exceeding the range specified above may lead to a reduced dispersibility in the resin, resulting in an increased viscosity of a resin composition or a poor appearance or mechanical property of a cured article.
  • a polymer fine particle (e) employed in the present invention has, as at least one inner layer, a polymer layer having a Tg not higher than 20° C., which exists in an amount of 50 to 95% by weight, preferably 70 to 90% by weight, based on the entire of a miltilayer-structured polymer.
  • An amount of the polymer layer having a Tg not higher than 20° C. less than the level specified above may lead to an insufficiently improved toughness or low thermal expansion performance of a resin composition, while an amount exceeding the level specified above may lead to a reduced dispersibility in the resin, resulting in an increased viscosity of a resin composition or a poor appearance or mechanical property of a hardened article.
  • a polymer fine particle (e) of the present invention preferably has the outermost layer whose Tg is 40° C. or higher. Absence of such an outermost layer makes it difficult to effect dispersion in the resin and to reduce the viscosity.
  • the particle size of a polymer fine particle (e) thus polymerized is usually 0.1 to 5.0 ⁇ m, preferably 0.2 to 2.0 ⁇ m.
  • a smaller particle size may increase the viscosity of a resin composition, and resulted in poor productivity of the resin, or insufficient improvement of the low thermal expansion performance. On the contrary, a larger particle size may lead to an insufficient toughness.
  • the particle size means a weight average particle size of a single particle of a multilayer-structured polymer in the state of a latex during the production of the multilayer-structured polymer, and can be measured by a dynamic light scattering method using a dynamic light scattering meter (for example, LPA-3000/LPA-3100, produced by OTSUKA DENSHI KK).
  • a polymer fine particle (e) of the present invention can be used in such a manner that a polymer latex polymerized by a method described above is once frozen and then thawed to separate the polymer particles and then centrifuged for dehydration and then dried and the resultant powder is dispersed in a mixture of resins (a) and (c), or it can be mixed in such a manner that the latex itself is placed in the starting material of the component (a) and the water is distilled off and then the component (a) is synthesized.
  • the amount of a polymer fine particle (e) employed in the present invention is usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
  • a curing agent is employed for curing a resin composition of the present invention.
  • Such a curing agent employed in the present invention may for example be organic peroxide such as methyl ethyl ketone peroxide, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide and cumene hydroperoxide.
  • the amount of a curing agent used is preferably 0.1 to 3 parts by weight based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
  • the Tg of a cured article obtained from a resin composition comprising such components (a), (b) and (c) is preferably 120° C. or higher, more preferably 135° C. or higher.
  • a fiber-reinforced layers impregnated with a thermosetting resin composition comprising the components (a), (b), (c) and (d) according to the present invention may be of any material employed conventionally for a laminated plate such as a glass non-woven fabric, glass woven fabric and paper substrate.
  • a laminated plate of the present invention can be obtained by overlaying three or more of fiber-reinforced layers impregnated with a thermosetting resin composition containing a curing agent to form a laminated material, covering the both sides if necessary with a metal foil such as a copper foil, and then curing the laminated material with heating and pressurizing.
  • a particularly preferred embodiment of the present invention is a combined laminated plate having as a impregnation substrate a glass fiber woven fabric, glass fiber non-woven fabric and paper substrate, namely, a composite laminated plate.
  • a composite laminated plate of the present invention obtained by curing and pressurizing a composite laminated material in which a glass fiber woven fabric impregnated with a thermosetting resin composition including the components (a), (b), (c) and (d) described above wherein the component (a) is present in an amount of 10 to 75 parts by weight, the component (b) is present in an amount of 2 to 30 parts by weight, the component (c) is present in an amount of 20 to 60 parts by weight and the component (d) is present in an amount of 5 to 250 parts by weight, based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight as a surface layer is laminated with a glass fiber non-woven fabric impregnated with a thermosetting resin composition comprising the components (a), (b
  • the linear expansion coefficient of a laminated plate of the present invention was measured by a thermal analyzer, and was a larger one of the vertical and lateral linear expansion coefficients of the laminated plate.
  • thermosetting resin composition comprising the components (a), (b), (c) and (d) employed in the present invention
  • a laminated plate having an extremely high heat resistance can be obtained.
  • an inventive laminated plate whose average linear expansion coefficient within the temperature range from 40 to 150° C. is not higher than 20.0 ⁇ 10 ⁇ 6 /° C., a low liner expansion coefficient which has not been achieved by a laminated plate employing a conventional radically polymerizable resin composition can be obtained for the first time.
  • a laminated plate of the present invention has excellent heat resistance and water resistance, exhibits a satisfactory punching performance, and has a low thermal expansion coefficient, it is applicable also to a use at a high temperature, such as in an automobile, to which a laminated plate made from a conventional liquid rubber component-containing thermosetting resin composition is not applicable.
  • a 1-L 5-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser whose top was equipped with a thermometer was charged with 438 g of adipic acid, 96 g of propylene glycol and 117 g of ethylene glycol, and was purged with nitrogen gas.
  • the mixture was subjected to dehydration condensation at 200° C. for 8 hours to obtain a saturated polyester resin whose acid value was 4.6 mg KOH/g (B-1).
  • the Tg and the number average molecular weigh of this resin were 42° C. and 24,400, respectively.
  • a 1-L 5-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser whose top was equipped with a thermometer was charged with 233 g of terephthalic acid, 113 g of azelaic acid, 65 g of ethylene glycol and 106 g of neopentyl glycol, and was purged with nitrogen.
  • the mixture was subjected to dehydration condensation at 240° C. for 10 hours to obtain a saturated polyester resin whose acid value was 1.4 mg KOH/g (B-2).
  • the Tg and the number average molecular weigh of this resin were 7° C. and 26900, respectively.
  • a 1-L 5-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser whose top was equipped with a thermometer was charged with 100 g of terephthalic acid, 66 g of isophthalic acid, 188 g of azelaic acid, 72 g of ethylene glycol and 96 g of neopentyl glycol, and was purged with nitrogen gas.
  • the mixture was subjected to dehydration condensation at 240° C. for 9 hours to obtain a saturated polyester resin whose acid value was 1.0 mg KOH/g (B-3).
  • the Tg and the number average molecular weigh of this resin were ⁇ 20° C. and 23900, respectively.
  • a 2-L g reactor for polymerization equipped with a condenser was charged with 506 g of deionized water, 2.4 g of a 1% aqueous solution of sodium dioctylsulfosuccinate and 16.4 g of a 1% aqueous solution of sodium hydrogen carbonate, and heated at 70° C. with stirring under a nitrogen stream. At elevated temperature, 8 g of ethyl acrylate was added and the mixture was stirred for 10 minutes, combined with 4.1 g of a 2% aqueous solution of sodium persulfate, and stirred for further 1 hour to obtain a seed latex.
  • a monomer emulsion for forming the first layer consisting of 663 g of butyl acrylate, 2.4 g of 1,4-butylene glycol diacrylate, 6.7 g of allyl methacrylate, 408 g of a 1% aqueous solution of sodium dioctylsulfosuccinate and 68 g of a 1% aqueous solution of sodium hydrogen carbonate was fed continuously over a period of 240 minutes. After feeding, the mixture was stirred further for 60 minutes at 70° C., for aging the reaction mixture.
  • a monomer emulsion for forming the outermost layer consisting of 7.2 g of a 2% aqueous solution of sodium persulfate was added followed by 101 g of methyl methacrylate, 12 g of ethyl acrylate, 0.6 g of 2-hydroxyethyl methacrylate, 6 g of 1,4-butylene glycol diacrylate, 60 g of a 1% aqueous solution of sodium dioctylsulfosuccinate and 12 g of a 1% sodium hydrogen carbonate was fed continuously over a period of 90 minutes.
  • the mixture After feeding, the mixture was heated further to 80° C., and stirred for 60 minutes for aging the reaction mixture. After the maturing reaction, the mixture was filtered through a 300-mesh stainless steel wire mesh to obtain a multilayer-structured polymer latex whose weight average particle size was 0.5 ⁇ m. This latex was frozen once at ⁇ 30° C., and then thawed, dehydrated and washed with a centrifuging dehydrator, and dried overnight at 40° C. under an air stream, whereby obtaining a multilayer-structured polymer fine particle (B-4).
  • thermosetting resin compositions 100 Parts by weight of each of the thermosetting resin compositions thus obtained was mixed with 40 parts by weight of aluminium hydroxide (CL-310, SUMITOMO CHEMICAL CO.
  • PCT Pressure Cooker Test
  • a laminated plate was measured in the vertical and lateral directions and the value giving a larger a was selected.
  • a laminated plate of the present invention has excellent heat resistance, water resistance and punching performance, can satisfactorily be used even with heating especially when it has a linear expansion coefficient within the temperature range from 40 to 150° C. of not higher than 20.0 ⁇ 10 ⁇ 6 /° C. It can be obtained at a low cost, when compared with a laminated plate made by a conventional method for example from an epoxy resin, without any deterioration in the quality of the final product when compared with a conventional product.

Abstract

A low thermal expansion laminated plate which has excellent heat resistance, water resistance and toughness and whose average linear expansion coefficient within the temperature ranging from 40 to 150° C. is not higher than 20×10−6/° C. can be obtained by laminating and curing fiber-reinforced layers impregnated with a resin composition consisting of a radically polymerizable resin, radically polymerizable monomer and inorganic filler combined with a specific amount of a thermoplastic resin.

Description

TECHNICAL FIELD
This application is a 371 of PCT/JP01/02382 filed Mar. 23, 2001.
The present invention relates to a laminated plate having a low thermal expansion and excellent toughness, heat resistance and water resistance, particularly to a composite laminated plate.
BACKGROUND ART
A cured article of a radically polymerizable resin such as unsaturated polyester resins or vinyl ester resins has a well-balanced performance with regard to the mechanical, chemical and electric characteristics, and has been employed widely in the fields of housing, shipping and automobile industries.
However, a cured article of such a radically polymerizable resin, when it is applied to a laminated plate for a print circuit board or a insulating plate while utilizing its excellent heat resistance, water resistance and electric characteristics, poses an insufficiency of the toughness and the impact resistance for the plate and undergoes problematic cracking or delamination between the fiber-reinforced layers during a punching process.
In an attempt to overcome such a problem, a liquid rubber component is added to the resin for enhancement of toughness, but a cured article of the resin containing a rubber component has a high thermal expansion rate, which is not always suitable for a laminated plate used under elevated temperature.
Accordingly, for the purpose of minimizing the thermal expansion rate of a cured article, a method was proposed in which a polymer fine particle is added to a radically polymerizable resin as disclosed in Japanese Patent Application Laid-open No.231654 (1996).
In this method, however, a large amount of the polymer fine particle should be added to the resin in order to obtain a sufficiently reduced thermal expansion. Unfortunately, such addition of the large amount of the polymer fine particle leads to an increase in the viscosity of the resin and the composition thereof, resulting in a new problem, which is a difficulty in producing the resin composition by a conventional method and apparatus.
An objective of the present invention is to provide a laminated plate, especially a composite laminated plate, which is obtained from a resin composition whose main component is a radically polymerizable resin, which has excellent toughness, heat resistance and water resistance, which has such a low thermal expansion rate as a average linear expansion coefficient (10−6/° C.) of not higher than 20 within the temperature range from 40 to 150° C., which can be processed and used at an elevated temperature, and which can be produced at a lower cost but can exert a performance comparable with a conventional expensive material such as an epoxy resin.
DISCLOSURE OF INVENTION
We made an effort to solve the problems described above, and discovered that a laminated plate obtained from a resin composition comprising a radical polymerizing resin combined with a specific amount of a thermoplastic resin can solve the problems described above, and then made a further effort to establish the present invention.
Thus, the present invention is:
1. A low thermal expansion laminated plate obtained by curing a laminated material of fiber-reinforced layers impregnated with a thermosetting resin composition comprising (a) a radically polymerizable resin, (b) a thermoplastic resin, (c) a radically polymerizable monomer and (d) an inorganic filler, wherein (a) is present in an amount of 10 to 75 parts by weight, (b) is present in an amount of 2 to 30 parts by weight, (c) is present in an amount of 20 to 60 parts by weight and (d) is present in an amount of 5 to 250 parts by weight, based on 100 parts by weight of the total weight of (a), (b) and (c).
2. A low thermal expansion laminated plate according to the above-mentioned 1 wherein the average linear expansion coefficient of the laminate within the temperature range from 40° C. to 150° C. is not higher than 20×10−6/° C.
3. A low thermal expansion laminated plate according to the above-mentioned 1 or 2 wherein the glass transition point of the thermoplastic resin (b) is not higher than 60° C.
4. A low thermal expansion laminated plate according to the above-mentioned 1 or 2 wherein the thermoplastic resin (b) is a saturated polyester resin whose glass transition point is not higher than 60° C.
5. A low thermal expansion laminated plate according to the above-mentioned 1 or 2 wherein the thermoplastic resin (b) is a saturated polyester resin whose glass transition point is not higher than 60° C. and whose number average molecular weight is 2,000 to 100,000.
6. A low thermal expansion laminated plate according to any one of the above-mentioned 1 to 5 further comprising a polymer fine particle (e) whose particle size is 0.1 to 5.0 μm.
7. A low thermal expansion laminated plate according to any one of the above-mentioned 1 to 6 wherein the laminated material of the fiber-reinforced layers is a composite laminated material comprising as a surface layer a glass fiber woven fabric impregnated with a thermosetting resin composition laminated with an inner lining layer which is a glass fiber non-woven fabric impregnated with a thermoplastic resin composition.
8. A low thermal expansion laminated plate according to any one of the above-mentioned 1 to 7 wherein the radically polymerizable resin (a) is a vinyl ester resin or unsaturated polyester resin.
9. A metal foil-covered laminated plate utilizing a low thermal expansion laminated plate according to any one of the above-mentioned 1 to 8.
While a radically polymerizable resin (a) employed in the present invention is not particularly limited as long as it is a resin having an ethylenically unsaturated bond, those employed preferably are a vinyl ester resins produced by adding ethylenically unsaturated monobasic acid to an epoxy resin and an unsaturated polyester resin produced by a dehydration condensation reaction between a dicarboxylic acid which should contain an α,β-olefinic unsaturated dicarboxylic acid or an anhydride thereof and a diol.
The epoxy resin as a starting material for a vinyl ester resin may for example be those disclosed in Japanese Patent Application Laid-open No.110948 (1997), such as a bisphenol epoxy resin including bisphenol A and bisphenol F, a novolac epoxy resin including phenol novolac [e.g., YDPN638, produced by TOTO KASEI CO. LTD., epoxy equivalent: 200] and cresol novolac [e.g., YDCN702P, produced by TOTO KASEI CO. LTD., epoxy equivalent: 200], an aliphatic epoxy resin, a nitrogen-containing epoxy resin (e.g., triglycidyl isocyanurate), a copolymeric epoxy resin and the like.
An ethylenically unsaturated monobasic acid may for example be an unsaturated monocarboxylic acid such as (meth)acrylic acid as well as a reaction product between a polybasic acid anhydride and a compound having at least one (meth)acrylic double bond and an alcoholic OH group simultaneously in one molecule.
A compound having at least one (meth)acrylic double bond and an alcoholic OH group simultaneously may for example be a reaction product between hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, pentaerythritol tri (meth)acrylate, glycerin di (meth)acrylate, (meth) acrylic acid and a polyhydric alcohol. Among those listed above, (meth)acrylic acid is preferred.
The reaction between an epoxy resin and an ethylenically unsaturated monobasic acid described above may be conducted by a known method. For example, the reaction is conducted at 80 to 150° C. for 1 to 20 hours in the presence of a polymerization inhibitor such as hydroquinone and a catalyst such as a tertiary amine e.g., benzyldimethylamine or a phosphorus compound e.g., triphenylphosphine, whereby obtaining an intended vinyl ester resin.
While the reaction between the epoxy group and the carboxyl group in the vinyl estrification reaction is a 1 to 1 equivalent reaction, the synthesis may sometimes be conducted also with an excess of the epoxy group or with an excess of the carboxyl group.
An unsaturated polyester resin employed in the present invention can be synthesized by condensation between an α,β-olefinic unsaturated dicarboxylic acid and a glycol. In addition to these two components, a saturated dicarboxylic acid, aromatic dicarboxylic acid or dicyclopentadiene capable of reacting with a dicarboxylic acid may also be employed in the synthesis of the unsaturated polyester resin.
An α,β-olefinic unsaturated dicarboxylic acid may for example be maleic acid, fumaric acid, itaconic acid, citraconic acid and anhydrides of these dicarboxylic acids. A dicarboxylic acid capable of being used together with such an α,β-olefinic unsaturated dicarboxylic acid may for example be adipic acid, sebacic acid, succinic acid, gluconic acid, o-, m-, p-phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and the like.
A glycol may for example be an alkane diol, oxa-alkane diol, a diol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A. In addition, a monohydric or trihydric alcohol may also be employed. An alkane diol may for example be ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, hydrogenated bisphenol A and the like. An oxa-alkane diol may for example be dioxyethylene glycol and triethylene glycol. A monohydric or trihydric alcohol used together with the glycols mentioned above may for example be octylalcohol, benzylalcohol, trimetylolpropane and the like.
The synthesis of an unsaturated polyester resin is conducted generally under heating, while water generated as a by-product being removed. Generally, the Tg of an unsaturated polyester resin can be lowered by selecting starting materials to reduce the crosslink density and the reactivity of the resin, or by starting from adipic acid or sebacic acid as a saturated acid and diethylene glycol or dipropylene glycol as a glycol, those have a long chain molecular structure. On the contrary, the Tg of the resin can be elevated by selecting starting material to increase the crosslink density or the reactivity of a resin or by starting from hydrogenated bisphenol A as a glycol which has a rigid structure.
The amount of a radically polymerizable resin (a) to be used is usually 10 to 75 parts by weight, preferably 30 to 67 parts by weight based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
The amount of a thermoplastic resin (b) employed in the present invention may for example be a thermoplastic resin used customarily as a low profile agent in an unsaturated polyester resin. Such a thermoplastic resin may for example be polybutadiene or a hydrogenated derivative thereof, polyisoprene or a hydrogenated derivative thereof, aromatic vinyl/conjugated diene block copolymer or a hydrogenated derivative thereof, polystyrene, styrene/vinyl acetate block copolymer, polyvinyl acetate, polymethyl methacrylate, as well as a saturated polyester resin, polyether resin and the like. Among those listed above, an aromatic vinyl/conjugated diene block copolymer and saturated polyester resin are preferred, with a saturated polyester resin being particularly preferred.
While the saturated polyester resin as a thermoplastic resin is not limited particularly, it preferably has a Tg of 60° C. or lower, more preferably 50° C. or lower. A Tg of the saturated polyester resin higher than 60° C. may be led to a difficulty in reducing the thermal expansion rate of a cured article sufficiently.
A saturated polyester resin may typically be those employed as single component anti-shrinkage agents for SMC and the like, for example, those synthesized from a dicarboxylic acid such as terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and the like and a diol such as ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexandiol, diethylene glycol, dipropylene glycol, and the like.
While the molecular weight of a saturated polyester resin is not limited particularly, the number average molecular weight is usually 2,000 to 100,000, preferably 3,000 to 30,000, since a too lower molecular weight leads to a reduced heat resistance while a too higher molecular weight leads to a high viscosity.
A saturated polyester resin may for example be TTK-101 (produced by TAKEDA CHEMICAL INDUSTRIES LTD.) and BYLON 300, 630, 550 (produced by TOYOBO CO., LTD.).
An aromatic vinyl/conjugated diene block copolymer is also a preferred example of the thermoplastic resin (b).
An aromatic vinyl/conjugated diene block copolymer may be a block copolymer known per se, and can be synthesized by block copolymerizing an aromatic vinyl monomer such as styrene, chlorostyrene and vinyl toluene with a conjugated diene monomer such as butadiene and isoprene by a conventional polymerization method. Such a block copolymer may for example be styrene/isoprene block copolymer. Such a block copolymer has a molar ratio of an aromatic vinyl monomer and a conjugated diene monomer of about 50:50 to 5:95 and an average molecular weight of about 30,000 to 200,000.
The amount of a thermoplastic resin (b) to be incorporated is usually 2 to 30 parts by weight, preferably 2 to 20 parts by weight based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
A radically polymerizable monomer (c) may for example be an unsaturated fatty acid such as acrylic acid and methacrylic acid, an unsaturated carboxylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-hydroxtethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and dodecyl acrylate, a nitrogen-containing monomer such as (meth)acrylamide and (meth)acrylonitrile, an aromatic vinyl compound such as styrene, vinyltoluene, divinylbenzene and p-t-butylstyrene and a polyfunctional (meth)acrylate such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate, any of which may be employed alone or in combination with each other. Among those listed above, styrene is particularly preferred.
The amount of a radically polymerizable monomer (c) to be incorporated is usually 20 to 60 parts by weight, preferably 25 to 55 parts by weight based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
An inorganic filler (d) employed in a thermosetting resin composition of the present invention may for example be aluminium hydroxide, glass powder, calcium carbonate, talc, silica, clay, glass balloon and the like. These may be used in an amount usually of 5 to 250 parts by weight, preferably 5 to 200 parts by weight, based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
The toughness and the low thermal expansion performance of a laminated plate can further be improved by incorporating a polymer fine particle (e) to a thermosetting resin composition employed in the present invention.
A polymer fine particle (e) preferably has a multilayer structure, although a monolayer particle may also be employed. Such a multilayer polymer fine particle can be obtained by a consecutive multi-stage emulsion polymerization in which, in the presence of the preceding stage polymer, the subsequent stage monomer is subjected sequentially to seed polymerization, as is disclosed in JP-A-8-48704. That is, seed latex is first prepared by emulsion polymerization, then a monomer for forming the first layer is added and subjected to the seed polymerization. Subsequently, a monomer for forming the second layer is added and subjected to the seed polymerization whereby synthesizing the second layer, and this procedure is repeated until the outermost layer is synthesized, whereby obtaining an intended multilayer-structured polymer.
A reactive unsaturated monomer employed in the seed polymerization of a polymer layer of a polymer fine particle (e) employed in the present invention may be any monomer having in the molecule thereof at least one reactive unsaturated bond, including a conjugated diene such as butadiene, isoprene and chloroprene, an alkyl acrylate such as ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, isononyl acrylate and 2-ethylhexyl acrylate and an alkyl methacrylate such as methyl methacrylate, ethyl methacrylate and cyclohexyl methacrylate. Any of these may be copolymerized with a monomer capable of being copolymerized with it, for example, an aromatic vinyl or aromatic vinylidene such as styrene, vinyltoluene and α-methylstyrene, a vinyl cyanide or vinylidene cyanide such as acrylonitrile and methacrylonitrile, an alkyl methacrylate such as methyl methacrylate and butyl methacrylate and an aromatic (meth) acrylate such as benzyl acrylate and phenoxyethyl acrylate.
In the polymerization of a polymer layer of a polymer fine particle, a specific amount of a crosslinking monomer and grafting monomer can be employed as a copolymeric monomer in addition to the monomers described above. The crosslinking monomer may be employed in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight based on the monomers forming the polymer, while the grafting monomer may be employed in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight based on the monomers forming the polymer layer.
A crosslinking monomer employed in the present invention is one having in its molecule at least two similar polymerizable groups, including an aromatic divinyl compound such as divinylbenzene and an alkane polyol polyacrylate or alkane polyol polymethacrylate such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimetacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate. Among those listed above, butylene glycol diacrylate and hexanediol diacrylate are particularly preferred.
A grafting monomer employed in the present invention has at least two polymerizable groups having a different reactivity from each other in its molecule, for example an unsaturated carboxylic acid allyl ester such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate. Among those mentioned above, allyl methacrylate is particularly preferred.
A polymer fine particle (e) employed in the present invention can serve to further improve the toughness of a resin composition by modifying the outermost layer with a carboxyl group- or hydroxy group-carrying monomer.
A carboxyl group-carrying monomer may for example be acrylic acid, methacrylic acid, maleic acid and itaconic acid. A hydroxy group-carrying monomer may for example be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 2-hydroxybutyl (meth)acrylate. Among those described above, methacrylic acid is a preferred carboxyl group-carrying monomer, while 2-hydroxyethyl methacrylate is a preferred hydroxyl group-carrying monomer.
The amount of such a functional group-carrying monomer is less than 10% by weight, preferably less than 5% by weight based on the monomers forming the outermost layer. An amount of the functional group carrying monomer exceeding the range specified above may lead to a reduced dispersibility in the resin, resulting in an increased viscosity of a resin composition or a poor appearance or mechanical property of a cured article.
A polymer fine particle (e) employed in the present invention has, as at least one inner layer, a polymer layer having a Tg not higher than 20° C., which exists in an amount of 50 to 95% by weight, preferably 70 to 90% by weight, based on the entire of a miltilayer-structured polymer. An amount of the polymer layer having a Tg not higher than 20° C. less than the level specified above may lead to an insufficiently improved toughness or low thermal expansion performance of a resin composition, while an amount exceeding the level specified above may lead to a reduced dispersibility in the resin, resulting in an increased viscosity of a resin composition or a poor appearance or mechanical property of a hardened article.
A polymer fine particle (e) of the present invention preferably has the outermost layer whose Tg is 40° C. or higher. Absence of such an outermost layer makes it difficult to effect dispersion in the resin and to reduce the viscosity.
The particle size of a polymer fine particle (e) thus polymerized is usually 0.1 to 5.0 μm, preferably 0.2 to 2.0 μm. A smaller particle size may increase the viscosity of a resin composition, and resulted in poor productivity of the resin, or insufficient improvement of the low thermal expansion performance. On the contrary, a larger particle size may lead to an insufficient toughness. The particle size means a weight average particle size of a single particle of a multilayer-structured polymer in the state of a latex during the production of the multilayer-structured polymer, and can be measured by a dynamic light scattering method using a dynamic light scattering meter (for example, LPA-3000/LPA-3100, produced by OTSUKA DENSHI KK).
A polymer fine particle (e) of the present invention can be used in such a manner that a polymer latex polymerized by a method described above is once frozen and then thawed to separate the polymer particles and then centrifuged for dehydration and then dried and the resultant powder is dispersed in a mixture of resins (a) and (c), or it can be mixed in such a manner that the latex itself is placed in the starting material of the component (a) and the water is distilled off and then the component (a) is synthesized.
The amount of a polymer fine particle (e) employed in the present invention is usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight.
A curing agent is employed for curing a resin composition of the present invention.
Such a curing agent employed in the present invention may for example be organic peroxide such as methyl ethyl ketone peroxide, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide and cumene hydroperoxide. The amount of a curing agent used is preferably 0.1 to 3 parts by weight based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight. The Tg of a cured article obtained from a resin composition comprising such components (a), (b) and (c) is preferably 120° C. or higher, more preferably 135° C. or higher.
A fiber-reinforced layers impregnated with a thermosetting resin composition comprising the components (a), (b), (c) and (d) according to the present invention may be of any material employed conventionally for a laminated plate such as a glass non-woven fabric, glass woven fabric and paper substrate.
A laminated plate of the present invention can be obtained by overlaying three or more of fiber-reinforced layers impregnated with a thermosetting resin composition containing a curing agent to form a laminated material, covering the both sides if necessary with a metal foil such as a copper foil, and then curing the laminated material with heating and pressurizing.
A particularly preferred embodiment of the present invention is a combined laminated plate having as a impregnation substrate a glass fiber woven fabric, glass fiber non-woven fabric and paper substrate, namely, a composite laminated plate. A composite laminated plate of the present invention obtained by curing and pressurizing a composite laminated material in which a glass fiber woven fabric impregnated with a thermosetting resin composition including the components (a), (b), (c) and (d) described above wherein the component (a) is present in an amount of 10 to 75 parts by weight, the component (b) is present in an amount of 2 to 30 parts by weight, the component (c) is present in an amount of 20 to 60 parts by weight and the component (d) is present in an amount of 5 to 250 parts by weight, based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight as a surface layer is laminated with a glass fiber non-woven fabric impregnated with a thermosetting resin composition comprising the components (a), (b), (c) and (d) described above wherein the component (a) is present in an amount of 10 to 75 parts by weight, the component (b) is present in an amount of 2 to 30 parts by weight, the component (c) is present in an amount of 20 to 60 parts by weight and the component (d) is present in an amount of 5 to 250 parts by weight, based on the total weight of the components (a), (b) and (c) being regarded as 100 parts by weight as an inner layer has excellent heat resistance, water resistance and toughness, and is extremely useful for a print circuit board.
The linear expansion coefficient of a laminated plate of the present invention was measured by a thermal analyzer, and was a larger one of the vertical and lateral linear expansion coefficients of the laminated plate.
When the Tg of a cured article obtained from a thermosetting resin composition comprising the components (a), (b), (c) and (d) employed in the present invention is 120° C. or higher, then a laminated plate having an extremely high heat resistance can be obtained. With an inventive laminated plate whose average linear expansion coefficient within the temperature range from 40 to 150° C. is not higher than 20.0×10−6/° C., a low liner expansion coefficient which has not been achieved by a laminated plate employing a conventional radically polymerizable resin composition can be obtained for the first time.
Since a laminated plate of the present invention has excellent heat resistance and water resistance, exhibits a satisfactory punching performance, and has a low thermal expansion coefficient, it is applicable also to a use at a high temperature, such as in an automobile, to which a laminated plate made from a conventional liquid rubber component-containing thermosetting resin composition is not applicable.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is further described in the following Synthetic Examples, Examples, Comparative Examples and Experiments, which are not intended to restrict the present invention.
SYNTHETIC EXAMPLE 1 Synthesis of Radically Polymerizable Resin
In a 2-L 4-necked flask equipped with a stirrer and a thermometer, 172 g of acrylic acid was added to 800 g of an epoxy resin (YDB-400, TOTO KASEI CO. LTD., epoxy equivalent: 400) was combined with 172 g of methacrylic acid in the presence of 0.3 g of hydroquinone and 0.3 g of benzyldimethylamine, and reacted at 120° C. for 6 hours to obtain a vinyl ester resin whose acid value was 2.0 mg KOH/g. Subsequently, 457 g of styrene monomer was added to obtain a vinyl ester resin (A-1) [NV (non-volatiles)=68%].
SYNTHETIC EXAMPLE 2 Synthesis of Radically Polymerizable Resin
In a 1-L 4-necked flask equipped with a stirrer and a thermometer, 374 g of an epoxy resin (YD-128, TOTO KASEI CO. LTD., epoxy equivalent: 187) was combined with 172 g of methacrylic acid in the presence of 0.3 g of hydroquinone and 0.3 g of benzyldimethylamine, and reacted at 120° C. for 6 hours to obtain a vinyl ester resin whose acid value was 2.0 mg KOH/g. Subsequently, 294 g of styrene monomer was added to obtain a vinyl ester resin (A2) (NV=65%).
SYNTHETIC EXAMPLE 3 Synthesis of Radically Polymerizable Resin
A 2-L 5-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser whose top was equipped with a thermometer was charged with 392 g of maleic anhydride, 141 g of propylene glycol and 0.07 g of hydroquinone, and was purged with nitrogen gas and subjected to dehydration condensation at 200° C. for 7 hours to obtain an unsaturated polyester resin whose acid value was 20.4 mg KOH/g. Subsequently, 649 g of styrene monomer was added to obtain an unsaturated polyester resin (A-3) (NV=48%).
SYNTHETIC EXAMPLE 4 Synthesis of Radically Polymerizable Resin
A 2-L 5-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser whose top was equipped with a thermometer was charged with 392 g of maleic anhydride, 239 g of propylene glycol, 141 g of dipropylene glycol and 0.07 g of hydroquinone, and was purged with nitrogen gas and subjected to dehydration condensation at 200° C. for 7 hours to obtain an unsaturated polyester resin whose acid value was 20.4 mg KOH/g. Subsequently, 649 g of styrene monomer was added to obtain an unsaturated polyester resin (A-4) (NV=48%).
SYNTHETIC EXAMPLE 5 Synthesis of Radically Polymerizable Resin
In a 3-L 4-necked flask equipped with a stirrer and a thermometer, 374 g of an epoxy resin (YD-128, TOTO KASEI CO. LTD., epoxy equivalent: 187) was combined with 971 g of a liquid rubber (CTBN, 1300×8, B.Goodrich) in the presence of 0.3 g of hydroquinone and 0.3 g of benzyldimethylamine, and reacted at 120° C. for 3 hours to obtain a rubber-modified epoxy resin whose acid value was 0.2 mg KOH/g and whose epoxy equivalent was 879. Then, 121 g of methacrylic acid was added and reacted at 120° C. for further 5 hours to obtain a rubber-modified vinyl ester resin whose acid value was 0.9 mg KOH/g. Subsequently, 977 g of styrene monomer was added to obtain a rubber-modified vinyl ester resin (A-5) (NV=60%.
SYNTHETIC EXAMPLE 6 Synthesis of Saturated Polyester Resin
A 1-L 5-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser whose top was equipped with a thermometer was charged with 438 g of adipic acid, 96 g of propylene glycol and 117 g of ethylene glycol, and was purged with nitrogen gas. The mixture was subjected to dehydration condensation at 200° C. for 8 hours to obtain a saturated polyester resin whose acid value was 4.6 mg KOH/g (B-1). The Tg and the number average molecular weigh of this resin were 42° C. and 24,400, respectively.
SYNTHETIC EXAMPLE 7 Synthesis of Saturated Polyester Resin
A 1-L 5-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser whose top was equipped with a thermometer was charged with 233 g of terephthalic acid, 113 g of azelaic acid, 65 g of ethylene glycol and 106 g of neopentyl glycol, and was purged with nitrogen. The mixture was subjected to dehydration condensation at 240° C. for 10 hours to obtain a saturated polyester resin whose acid value was 1.4 mg KOH/g (B-2). The Tg and the number average molecular weigh of this resin were 7° C. and 26900, respectively.
SYNTHETIC EXAMPLE 8 Synthesis of Saturated Polyester Resin
A 1-L 5-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser whose top was equipped with a thermometer was charged with 100 g of terephthalic acid, 66 g of isophthalic acid, 188 g of azelaic acid, 72 g of ethylene glycol and 96 g of neopentyl glycol, and was purged with nitrogen gas. The mixture was subjected to dehydration condensation at 240° C. for 9 hours to obtain a saturated polyester resin whose acid value was 1.0 mg KOH/g (B-3). The Tg and the number average molecular weigh of this resin were −20° C. and 23900, respectively.
SYNTHETIC EXAMPLE 9 Synthesis of Fine Particle of Multilayer-Structured Polymer
A 2-L g reactor for polymerization equipped with a condenser was charged with 506 g of deionized water, 2.4 g of a 1% aqueous solution of sodium dioctylsulfosuccinate and 16.4 g of a 1% aqueous solution of sodium hydrogen carbonate, and heated at 70° C. with stirring under a nitrogen stream. At elevated temperature, 8 g of ethyl acrylate was added and the mixture was stirred for 10 minutes, combined with 4.1 g of a 2% aqueous solution of sodium persulfate, and stirred for further 1 hour to obtain a seed latex. Subsequently, 51 g of a 2% aqueous solution of sodium persulfate was added at 70° C., and then a monomer emulsion for forming the first layer consisting of 663 g of butyl acrylate, 2.4 g of 1,4-butylene glycol diacrylate, 6.7 g of allyl methacrylate, 408 g of a 1% aqueous solution of sodium dioctylsulfosuccinate and 68 g of a 1% aqueous solution of sodium hydrogen carbonate was fed continuously over a period of 240 minutes. After feeding, the mixture was stirred further for 60 minutes at 70° C., for aging the reaction mixture. Then, to the mixture which was still kept at 70° C., a monomer emulsion for forming the outermost layer consisting of 7.2 g of a 2% aqueous solution of sodium persulfate was added followed by 101 g of methyl methacrylate, 12 g of ethyl acrylate, 0.6 g of 2-hydroxyethyl methacrylate, 6 g of 1,4-butylene glycol diacrylate, 60 g of a 1% aqueous solution of sodium dioctylsulfosuccinate and 12 g of a 1% sodium hydrogen carbonate was fed continuously over a period of 90 minutes. After feeding, the mixture was heated further to 80° C., and stirred for 60 minutes for aging the reaction mixture. After the maturing reaction, the mixture was filtered through a 300-mesh stainless steel wire mesh to obtain a multilayer-structured polymer latex whose weight average particle size was 0.5 μm. This latex was frozen once at −30° C., and then thawed, dehydrated and washed with a centrifuging dehydrator, and dried overnight at 40° C. under an air stream, whereby obtaining a multilayer-structured polymer fine particle (B-4).
EXAMPLES 1 TO 6 AND COMPARATIVE EXAMPLES 1 AND 2
The radically polymerizable resins (A-1) to (A-5) obtained in Synthetic Examples 1 to 5 in the amounts specified in Table 1, which were warmed at 80° C., were combined with the saturated polyester resins (B-1) to (B-3) and the polymer fine particle (B-4) obtained in Synthetic Examples 6 to 9, and dissolution was effected at 80° C. over a period of 3 hours, whereby obtaining thermosetting resin compositions. 100 Parts by weight of each of the thermosetting resin compositions thus obtained was mixed with 40 parts by weight of aluminium hydroxide (CL-310, SUMITOMO CHEMICAL CO. LTD.) and 1.0 parts by weight of 80% cumene hydroperoxide (PARKMIL H-80, NOF CORPORATION) to form Compound (1), or mixed with 140 parts by weight of aluminium hydroxide and 1.0 parts by weight of 80% cumene hydroperoxide to form Compound (2).
One layer of a glass fiber woven fabric for a laminated plate (WE-18K-BS, NITTO BOSEKI CO.) impregnated with Compound (1), three layers of a glass fiber non-woven fabric (Ep-4060, 60 g/m2, JAPAN VILENE CO., LTD.) impregnated with Compound (2) and one layer of a glass fiber woven fabric (WE-18K-BS, NITTO BOSEKI CO.) impregnated with Compound (1) were laminated in this order, and cured at 100° C. for 30 minutes under pressure and 175° C. for 30 minutes to obtain a laminated plate with dimension of 150×150×1.6 mm.
Experiment 1
Each laminated plate obtained in Examples and Comparatives was examined for the items listed below, and the physical parameters obtained are indicated in Table 1 together with its starting materials of the resin.
(1) Pressure Cooker Test (PCT)
Sample: Laminated plate cut into a size of 40 mm×40 mm piece
Condition: 121° C.×95% RH×60 minutes
% Water absorption: Calculated as follows:
% Water absorption=(Post-PCT weight-initial weight)/Initial weight×100
260° C. solder heat resistance test: Post-PCT sample was immersed in a molten solder bath (260±5° C.) and the time period (sec) until a blister was formed was recorded.
(2) Linear Expansion Coefficient (Hereinafter Abbreviated as “α”) measurement
A laminated plate was measured in the vertical and lateral directions and the value giving a larger a was selected.
Sample: Plate of glass fiber woven fabric cut into a 3 mm×15 mm
Instrument: Thermal analyzer (5 g load, elevated by 5° C./min, measured from 20 to 200° C., average linear expansion coefficient from 40 to 150° C.)
(3) Punching Performance
In accordance with ASTM D617
Evaluation:
Excellent: ◯
Good: Δ
Acceptable: x
TABLE 1
Comparative
Examples Examples
1 2 3 4 5 6 1 2
Radically A-1 50 50 15 50 50 50 50 50
polymeriz- A-2 15.3 15.3 31.4 13 12 15.3
able resin A-3 15 18 40 30 20
(% by A-4 18 15
weight) A-5 30
Styrene monomer (% by weight) 4.7 4.7 9.6 4.7
Thermoplas- Saturated polyester B-1 15 10
tic resin (% resin B-2 12 10 12
by weight) B-3 9
Polymer fine particle B-4 2 5
PCT Water absorption (%) 0.28 0.25 0.24 0.26 0.24 0.21 0.36 0.30
260° C. Solder >180 >180 >180 >180 >180 >180 >180 >180
heat resistance (sec)
Linear expansion coefficient α (10−6/° C.) 187 15.2 19.0 17.6 16.0 19.6 30.5 25.4
Punching performance ◯ ◯ ◯ ◯ ◯ ◯ ◯ X
As evident from Table 1, the linear expansion coefficient α (10−6/° C.) of each inventive laminated plate was as low as 20 or less, while that of Comparative 1 or 2 employing no saturated polyester resin was as high as 25. The punching performance of each laminated plate of Examples was also markedly excellent when compared with Comparatives.
INDUSTRIAL APPLICABILITY
A laminated plate of the present invention has excellent heat resistance, water resistance and punching performance, can satisfactorily be used even with heating especially when it has a linear expansion coefficient within the temperature range from 40 to 150° C. of not higher than 20.0×10−6/° C. It can be obtained at a low cost, when compared with a laminated plate made by a conventional method for example from an epoxy resin, without any deterioration in the quality of the final product when compared with a conventional product.

Claims (9)

What is claimed is:
1. A low thermal expansion laminated plate obtained by curing a laminated material of fiber-reinforced layers impregnated with a thermosetting resin composition comprising a radically polymerizable resin (a), a thermoplastic resin (b), a radically polymerizable monomer (c) and an inorganic filler (d), wherein (a) is present in an amount of 10 to 75 parts by weight, (b) is present in an amount of 2 to 30 parts by weight, (c) is present in an amount of 20 to 60 parts by weight and (d) is present in an amount of 5 to 250 parts by weight, based on 100 parts by weight of the total weight of (a), (b) and (c).
2. A low thermal expansion laminated plate according to claim 1 wherein the average linear expansion coefficient of the laminate within the temperature ranging from 40° C. to 150° C. is not higher than 20×10−6/° C.
3. A low thermal expansion laminated plate according to claim 1 wherein the glass transition point of the thermoplastic resin (b) is not higher than 60° C.
4. A low thermal expansion laminated plate according to claim 1 wherein the thermoplastic resin (b) is a saturated polyester resin whose glass transition point is not higher than 60° C.
5. A low thermal expansion laminated plate according to claim 1 wherein the thermoplastic resin (b) is a saturated polyester resin whose glass transition point is not higher than 60° C. and whose number average molecular weight is 2,000 to 100,000.
6. A low thermal expansion laminated plate according to claim 1 further comprising a polymer fine particle (e) whose particle size is 0.1 to 5.0 μm.
7. A low thermal expansion laminated plate according to claim 1 wherein the laminated material of the fiber-reinforced layers is a composite laminated material comprising as a surface layer a glass fiber woven fabric impregnated with a thermosetting resin composition laminated with an inner lining layer which is a glass fiber non-woven fabric impregnated with a thermoplastic resin composition.
8. A low thermal expansion laminated plate according to claim 1 wherein the radically polymerizable resin (a) is a vinyl ester resin or unsaturated polyester resin.
9. A metal foil-covered laminated plate utilizing a low thermal expansion laminated plate according to claim 1.
US10/221,373 2000-03-27 2001-03-23 Lowly heat-expandable laminate Expired - Lifetime US6815053B2 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2000-087330 2000-03-27
JP2000087330 2000-03-27
JP2000-087329 2000-03-27
JP2000087329 2000-03-27
JP2000-87329 2000-03-27
JP2000-87330 2000-03-27
PCT/JP2001/002382 WO2001072879A1 (en) 2000-03-27 2001-03-23 Lowly heat-expandable laminate

Publications (2)

Publication Number Publication Date
US20040096680A1 US20040096680A1 (en) 2004-05-20
US6815053B2 true US6815053B2 (en) 2004-11-09

Family

ID=26588482

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/221,373 Expired - Lifetime US6815053B2 (en) 2000-03-27 2001-03-23 Lowly heat-expandable laminate

Country Status (8)

Country Link
US (1) US6815053B2 (en)
EP (1) EP1275682B1 (en)
JP (1) JP4779129B2 (en)
KR (1) KR100719866B1 (en)
CN (1) CN1205257C (en)
AT (1) ATE381588T1 (en)
DE (1) DE60131958T2 (en)
WO (1) WO2001072879A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE44893E1 (en) 2004-03-26 2014-05-13 Hanwha Azdel, Inc. Fiber reinforced thermoplastic sheets with surface coverings
US10266292B2 (en) 2015-01-22 2019-04-23 Neptune Research, Llc Carriers for composite reinforcement systems and methods of use

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4595430B2 (en) * 2004-07-30 2010-12-08 パナソニック電工株式会社 Printed wiring board substrate for mounting LEDs
JP4595429B2 (en) * 2004-07-30 2010-12-08 パナソニック電工株式会社 Laminated board for printed wiring board mounting LED
DE602006015781D1 (en) * 2005-03-15 2010-09-09 Sekisui Chemical Co Ltd METHOD FOR PRODUCING AN APPROPRIATE THERMOPLASTIC POLYESTER RESIN FOIL
US8722191B2 (en) * 2006-03-03 2014-05-13 Sumitomo Bakelite Co., Ltd. Intermediate layer material and composite laminate
WO2009028110A1 (en) * 2007-08-24 2009-03-05 Sumitomo Bakelite Co., Ltd. Multilayered wiring board and semiconductor device
FR2934198B1 (en) * 2008-07-24 2012-12-21 Eads Europ Aeronautic Defence PLI AND METHOD FOR METALLIZING A PIECE OF COMPOSITE MATERIAL.
JP5505304B2 (en) * 2009-03-16 2014-05-28 東レ株式会社 Fiber-reinforced resin composition, molding material, and method for producing fiber-reinforced resin composition
JP2012025122A (en) * 2010-07-27 2012-02-09 Panasonic Electric Works Co Ltd Method for manufacturing fiber-reinforced plastic plate
JP5752078B2 (en) * 2012-03-30 2015-07-22 ユニ・チャーム株式会社 Nonwoven fabric and method for producing nonwoven fabric
CN104889677A (en) * 2015-04-30 2015-09-09 燕山大学 Method for preparing stainless steel/carbon steel cutting core composite structural steel
TW202110995A (en) * 2019-07-08 2021-03-16 日商Ｄｉｃ股份有限公司 Resin composition, prepreg, laminated plate, multilayer printed wiring board, and semiconductor package

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549586A (en) 1969-04-01 1970-12-22 Union Carbide Corp Polyester compositions
US3936575A (en) * 1973-02-21 1976-02-03 Sumitomo Bakelite Company, Limited Flexible metal-clad laminates and method for manufacturing the same
EP0217311A2 (en) 1985-09-27 1987-04-08 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Glass fiber-reinforced electrical laminates and a continuous production method therefor
JPH07268196A (en) 1994-03-31 1995-10-17 Matsushita Electric Works Ltd Unsaturated polyester resin forming material
JPH08231654A (en) 1995-02-27 1996-09-10 Matsushita Electric Works Ltd Resin composition for laminate and copper-clad laminate made by using same
JPH08259778A (en) 1995-03-23 1996-10-08 Matsushita Electric Works Ltd Resin composition for laminate and copper-clad laminate using the same
JPH08318593A (en) 1995-05-25 1996-12-03 Matsushita Electric Works Ltd Production of copper clad laminated sheet
US5830548A (en) * 1992-08-11 1998-11-03 E. Khashoggi Industries, Llc Articles of manufacture and methods for manufacturing laminate structures including inorganically filled sheets
US5928767A (en) 1995-06-07 1999-07-27 Dexter Corporation Conductive film composite
JP2000080260A (en) 1998-09-03 2000-03-21 Showa Highpolymer Co Ltd Thermosetting resin composition set to have both flexibility and heat resistance
US6352782B2 (en) * 1999-12-01 2002-03-05 General Electric Company Poly(phenylene ether)-polyvinyl thermosetting resin
US6605343B1 (en) * 1999-02-22 2003-08-12 Sekisui Chemical Co., Ltd. Composite material and synthetic sleeper using the composite material

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549586A (en) 1969-04-01 1970-12-22 Union Carbide Corp Polyester compositions
US3936575A (en) * 1973-02-21 1976-02-03 Sumitomo Bakelite Company, Limited Flexible metal-clad laminates and method for manufacturing the same
EP0217311A2 (en) 1985-09-27 1987-04-08 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Glass fiber-reinforced electrical laminates and a continuous production method therefor
US5830548A (en) * 1992-08-11 1998-11-03 E. Khashoggi Industries, Llc Articles of manufacture and methods for manufacturing laminate structures including inorganically filled sheets
JPH07268196A (en) 1994-03-31 1995-10-17 Matsushita Electric Works Ltd Unsaturated polyester resin forming material
JPH08231654A (en) 1995-02-27 1996-09-10 Matsushita Electric Works Ltd Resin composition for laminate and copper-clad laminate made by using same
JPH08259778A (en) 1995-03-23 1996-10-08 Matsushita Electric Works Ltd Resin composition for laminate and copper-clad laminate using the same
JPH08318593A (en) 1995-05-25 1996-12-03 Matsushita Electric Works Ltd Production of copper clad laminated sheet
US5928767A (en) 1995-06-07 1999-07-27 Dexter Corporation Conductive film composite
JP2000080260A (en) 1998-09-03 2000-03-21 Showa Highpolymer Co Ltd Thermosetting resin composition set to have both flexibility and heat resistance
US6605343B1 (en) * 1999-02-22 2003-08-12 Sekisui Chemical Co., Ltd. Composite material and synthetic sleeper using the composite material
US6352782B2 (en) * 1999-12-01 2002-03-05 General Electric Company Poly(phenylene ether)-polyvinyl thermosetting resin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE44893E1 (en) 2004-03-26 2014-05-13 Hanwha Azdel, Inc. Fiber reinforced thermoplastic sheets with surface coverings
US10266292B2 (en) 2015-01-22 2019-04-23 Neptune Research, Llc Carriers for composite reinforcement systems and methods of use
US10597182B2 (en) 2015-01-22 2020-03-24 Neptune Research, Llc. Composite reinforcement systems and methods of manufacturing the same
US11453518B2 (en) 2015-01-22 2022-09-27 Csc Operating Company, Llc Composite reinforcement systems and methods of manufacturing the same

Also Published As

Publication number Publication date
ATE381588T1 (en) 2008-01-15
CN1419581A (en) 2003-05-21
EP1275682A1 (en) 2003-01-15
DE60131958D1 (en) 2008-01-31
EP1275682A4 (en) 2003-07-16
JP4779129B2 (en) 2011-09-28
EP1275682B1 (en) 2007-12-19
JPWO2001072879A1 (en) 2004-01-08
DE60131958T2 (en) 2008-12-11
CN1205257C (en) 2005-06-08
US20040096680A1 (en) 2004-05-20
KR20020093004A (en) 2002-12-12
KR100719866B1 (en) 2007-05-21
WO2001072879A1 (en) 2001-10-04

Similar Documents

Publication Publication Date Title
US6815053B2 (en) Lowly heat-expandable laminate
WO2014115778A1 (en) Curable resin composition containing polymer microparticles
WO1999014272A1 (en) Acrylic films and acrylic laminates
JP5285887B2 (en) Epoxy resin composition, method for continuously producing metal-clad laminate, and metal-clad laminate
JP5058571B2 (en) Thermosetting resin composition for copper clad laminate, copper clad laminate, and method for producing copper clad laminate
JP4595429B2 (en) Laminated board for printed wiring board mounting LED
JP4916015B2 (en) Liquid thermosetting resin composition, resin cured product, copper-clad laminate, and method for producing copper-clad laminate
EP2316883B1 (en) Unsaturated ester resin composition, unsaturated ester-cured product, and manufacturing method therefor
JP4911975B2 (en) Conductive resin composition and fuel cell separator
JP2005007783A (en) Halogen-free low-thermal-expansion composite laminate
JP3263164B2 (en) Unsaturated polyester resin composition and molding material for molded articles of automobile exterior parts excellent in paintability, and molded articles of automobile exterior parts excellent in paintability
CN109071738B (en) Radically curable resin composition and cured product thereof
JP4964722B2 (en) Continuously produced thermosetting resin composition for copper-clad laminate, copper-clad laminate production method, and copper-clad laminate
JP4416347B2 (en) Thermosetting resin composition and cured product thereof
JP2002284825A (en) Resin composition for laminate and laminate prepared by using the same
JP2020036011A (en) Method for manufacturing multilayer printed wiring board, resin film and multilayer printed wiring board
WO2023145471A1 (en) Resin composition, prepreg, resin-equipped film, resin-equipped metal foil, metal-cladded laminated board, and printed wiring board
JP2000309697A (en) Flame-retardant unsaturated polyester, resin containing the same, and cured product thereof
JP4595430B2 (en) Printed wiring board substrate for mounting LEDs
JPH02300220A (en) Allylic thermosetting resin composition
JPS61275347A (en) Unsaturated polyester resin composition and laminated sheet
WO2000050486A1 (en) Flame-retardant unsaturated polyester resin
JP2000072829A (en) Resin composition
JPH04132714A (en) Thermosetting resin composition
JP2001002770A (en) Flame-retardant unsaturated polyester resin and composition containing the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: MATSUSHITA ELECTRIC WORKS, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HIRATA, ISAO;OKADA, SHIGEHIRO;REEL/FRAME:013468/0014

Effective date: 20020820

Owner name: MITSUI TAKEDA CHEMICALS, INC., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:INOUE, TOMOKO;OKUMURA, HIROYA;REEL/FRAME:013468/0065

Effective date: 20020812

AS Assignment

Owner name: JAPAN COMPOSITE CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MITSUI TAKEDA CHEMICALS INC.;REEL/FRAME:015166/0476

Effective date: 20040324

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: PANASONIC ELECTRIC WORKS CO., LTD., JAPAN

Free format text: CHANGE OF NAME;ASSIGNOR:MATSUSHITA ELECTRIC WORKS, LTD.;REEL/FRAME:022191/0478

Effective date: 20081001

Owner name: PANASONIC ELECTRIC WORKS CO., LTD.,JAPAN

Free format text: CHANGE OF NAME;ASSIGNOR:MATSUSHITA ELECTRIC WORKS, LTD.;REEL/FRAME:022191/0478

Effective date: 20081001

FPAY Fee payment

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 12